Method of killing microorganisms, plant pests, and plants with halogenated dihydrothiophene-1, 1-di-oxide compounds



United States Patent Ofifice 3,073,692 Patented Jan. 15, 1963 ofDelaware No Drawing. Filed Feb. 23, 1960, Ser. No. 10,037 17 71-25)Claims. (Cl.

wherein X is a halogen, such as fluorine, chlorine, bromine or iodine,chlorine being preferred, m is a number from 3 to 6, inclusive, and n isa number equal to (6-m), in pesticidal' applications.

Illustrative of specific compounds employed in the practice of thepresent invention are:

3,3,4,5-tetrachloro-2,3-dihydrothiophene-1,1-dioxide 01 01 CHE-4 Hit)(J-Cl 3,3,4-trichloro-2,3-dihydrothiophene-l,l-dioxide 3,3,5-trichloro-2,3-dihydrothiophene-1,1-di0xide3,4-dichloro2,3-dihydrothiophene-1,1-dioxide H: CH

Compounds of the above structure generally exhibit a marked degree ofbiological activity and are useful in a variety of applications such asfungicides, bactericides, miticides, insecticides, herbicides, soilfungicides, seed protectants, and the like as will be described in moredetail hereinafter.

' such as a lower As used in the specification and claims, the termspesticide and pesticidal are meant to refer to the killing and/orcontrolling of the growth of plants, insects, nematodes, microoganisms,fungi, bacteria, or the like. Thus,'it will be appreciated thatapplications commonly termed herbicidal, insecticidal, bactericidal,fungicidal, enmatocidal, or the like, are contemplated.

Novel compounds of this invention as defined by the above-indicatedgeneric formula generally may be prepared by monodehydrohalogenation ofa compound of the formula: J3

wherein m is a number from 3 to 6, inclusive, and n is a number equal to(6-m). Generally, the monodehydrohalogenation, preferablymonodehydrochlorination, of to tetratoheptachlorotetrahydrothiophene-l,l-dioxide, to obtain a novel compoundof this invention is carried out in an organic solvent, usually underalkaline conditions, e.g., as by the addition of a small amount ofpyridine. A preferred practice comprises dissolving the compound to bemonodehydrohalogenated in a solvent, alkyl alcohol, containing a smallamount an elevated temperature, e.g., the boiling temperature of theorganic solvent, and thereafter separating the product, as by addingwater to the hot alcoholic solution and cooling the resultant mixture,or by solvent removal.

In order that those skilled in the art may more completely understandthe present invention and the preferred methods by which the same may becarried into effect, the following specific examples are offered:

of 'a soluble base, at

EXAMPLE I Part A PREPARATION OF 3,3,4,5-TETRACHLORO-2,3-DIHYDRO-THIOPHENE-1,1-DIOXIDE tions from petroleum ether weigh 51.0 g. (M.P.70.5-

72 C.). Elemental analysis indicates formation of desired C H Cl O S andis as follows:

Calculated, Percent by Weight Element In the following references totest formulations, aqueous formulations of the indicated concentrationsare intended unless otherwise indicated; these formulations are preparedby mixing the toxicant in water, usually employing a solvent, e.g., 5%acetone and an emulsifier, e.g., Triton X-l55 (alkyl aryl polyetheralcohol).

3. Part B.

The product of Part A is evaluated as a toxicant against the Germancockroach. and Mexican bean beetle as follows:

(a) German cockroaches (Blattella germanica) 8-9 weeksold areanaesthetized with carbon dioxide to facili: tate handling and aredipped into test formulations of the. product of Part A (2000 p.p.m. and1000 p.p.m.) for 10. seconds, removed, freed of excessive liquid andcaged. Two lots of. insects each are so treated. Mortality observationsafter three days indicate 100% morality at' the 2000 p.p.m.concentration and5100% mortality at.

the 1000 p.p.m. concentration.

(b) Fourth instar larvae of the Mexican bean beetle (Epilachnavarivestis) less than one day old within the instar are employed. Pairedseed leaves excised from Tendergreen bean plants are dipped into testformulations of the product of PartA (2000 p.p.m. and 1000 p.p.m.) untilthey are thoroughly wetted and then are allowed to dry. Each leaf isplaced in a 9 cm. Petri dish with a filter paper liner and 10 randomlyselected larvae are introduced. After three days exposure, it isobserved that 100% mortality occurred at the 2000'p.p.m.v concentrationand 100% mortality occurred at the 1000 p.p.m. concentration.

Part C.

To. demonstrate fungicidal elfectivenessyof. compounds. of thisinvention, germinationtests are conducted using the product-of Part'A ofthis example viathe. procedure. recommended by the American.Phytopathological Society. This procedure comprises usingformulations-containing the product of Part. A in concentrations. (priorto dilution of 4 volumes with 1 volume ofspore stimulant: and,spore;suspension) of 1000, 100, 10.. and-;1,p.p.'m., respectively, intests therewith to inhibit spore germination. More specifical-. 1y,spores. from 7-10 day old culturessofAltemaria oleracea and Monoliniafructicola are contacted with the test fungicide. It is observed thatthe product of Part A has an ED 50 value, i.e., the concentration whichinhibits germination of one half the spores in the test drops, regardingboth the A. oleraceaand M. fructicola of 0.01 to 0.1 p.p.nr. or less,and the same for the M. fructicola; This is better than thecorresponding 'ED 50 value of 1-10 p.p.m. exhibited by copper sulfateemployed as a standard reference material.

Part D To demonstrate the ability of the product of Part A to inhibitseed germination, tests are conducted using perennial rye grass andradish seed. These seeds are p.p.m. are thus obtained with respect toeach type of. seed, demonstrating a high degree of seed germination.

inhibition.

Part E To evaluate the effect of the tests of the product of Part A uponthe germination of seeds-in soil, a mixture.

of seed of six crop plants is placed in 8" x 8" x 2" metal cake panfilled to within one half inch of the top with greenhouse soil. The seedis uniformly covered with about one quarter inch of 'soil and watered;After 24 wherein organisms: are. contacted.

hours, ..rnl. of an aqueous test formulation, containing the below shownamounts of the product of Part A, uniformly is sprayed at 10 pounds airpressure over the surface of the pan. Thisaisrequivalent to the belowshown pounds. per acre. The seed:rnixture contains representativesof 3Broadleaf plants (turnip, flax and alfalfa), and 3 grasses (wheat,milletand rye).

Broadleaf Dosage, Pounds per Acre Grass Tests are conducted todemonstrate herbicidal activity of the product-of Part A, both viadirect action, e.g., by spraying foliage, and by soil watering tests. Inthe foliage spray test (No. 1) tomato plants of the variety Bonny Best,5-7 inches tall; (No. 2) corn of the variety Cornell M-l (field corn 4-6inches tall); (No. 3) beans of the variety Tendergreen; and (No. 4) oatsof the variety Clinton are sprayed with ml. portions of a testformulation of the product of Part A at a concentration of 6400 ppm.After the sprayed plants are dried, they are removed to a greenhousewherethey are observed 14 days after treat ment.

Phytotoxicity is rated on a scale from 0-11, 11 indicat ing completekill. Asa .resultof the test on tomato, bean, corn, and oats, values of11, 11, 2 and 3 are observed, rsepectively, indicating selective action.

In soil watering tests tomato and bean plants of about the same size andvariety as used in a spray test are treated by pouring 51 ml. of a 2000p.p.m. test formulation of the product of-Part A into 4 inch pots ofsoil containing the plants (corresponding to 128 pounds per acre). Atthe concentrations used, it is observed that the tomato plants arekilled and the bean plants receive a rating of 5.

Part G To indicate the nematocidal effectiveness of the product of PartA, further tests are conducted to illustrate effectiveness as a contactpoison against nematodes using the nematode species Panagrellusredivivus. In this procedure, the nematodes are exposed to the productof Part A while in small watch glasses (27 mm. in diameter x 8 mm. deep)disposed in a 9 cm. Petri dish.

Using this procedure, fumigant action is demonstrated by placing inthree separatePetri dishes, 64, 32 and 16 mg. per dish. Using theseconcentrations, after 24 hours, percentage mortality values of 86%, 66%and 8%, respectively, are observed.

Part H Part I Tests are carried out.,to determine the effectiveness ofPart A m protecting cucumber seeds from the product of seed decay anddamping 01f fungicide. Using the prodnet of Part A, the mean percentagestand at various dosby systemic action as indicated.

ages of active ingredients, expressed as percent of seed weight are asfollows:

Part I To illustrate the effectiveness of the product of Part A as ananti-fungal seed protectant, the compound is formulated as a 5% dustusing pyrophyllite as a carrier. Pea seeds are then treated with thisformulation at 3 different dosages, i.e., 0.018, 0.006 and 0.002% activeingredients, based on seed weight. Eight replications of each dosage areset up in Pythium-infested soil using 25 seeds per replicate. Theresults obtained are:

l 0.12 percent by seed weight =1.08 oz./bushel of peas or 0.0625 percentby seed Weight=1 oz./100 lbs. of seed.

Part K To demonstrate furnigant fungicidal activity, a technique is usedsimilar to that employed in Part F of this example, wherein a 9 cm.Petri dish is employed as a test chamber. A spore suspension (/2 ml. induplicate small watch glasses 27 mm. diameter x 8 mm. deep) is placed inthe Petri dish with the product of Part A contained in a separateidentical watch glass and the lid is closed.

Records on inhibition of spore germination are taken after D 18 hours.Against Alternaria oleracea, concentrations as low as 4 micrograms pertest dish completely inhibit spore germination.

Another example of the ability of the product of Part A of this exampleto protect tomato foliage from early blight by fumigant action isdemonstrated in the following procedure: tomato plants exposed to sporesuspension, Alternaria solani, were placed under inverted battery jarsin a pan of water. Small watch glasses containing the prodnet of Part A,evaporated from an acetone solution, were Placed on the soil under theplants growing in 4 inch clay pots. The battery jars serve as individualmoist chambers so infection occurs. Under these test conditions and at aconcentration of 64 micrograms of test compound per battery jar theearly blight is completely controlled.

anol containing 0.581 mol pyridine for 10 minutes and the resultingsolution poured into 3 liters of water. After 6 severalrecrystallizations from a benzenecyclohexane mixture, 40.8 g. of whitecrystals melting at 1085-1095 C. are obtained. Elemental analysisindicates preparation of the desired C H Cl O S and is as follows:

Actual, per- Calculated, Element cent by percent by Weight Weight Part BInsecticidal utility for the product of Part A of this example is shownin the following tests:

(a) Using the same Mexican bean beetle test proce-' dure given in Part Bof Example I, the product of Part A of this example at a concentrationof 2000 p.p.m. caused 100% mortality.

(b) 10 ml. of the above test material at a concentration of 2000 ppm. asan aqueous formulation, containing 10% sugar is placed on a piece ofcellucotton. 25 house flies, 45 days old, are caged over thethus-treated cellucotton and mortality counts are made after 24 hours.The results of the test show 28% mortality.

Part C Using the product of Part A of this example to show fungicidalactivity, the tests described in Part C of Example I are carried out.Using this procedure, the product of Part A of this example exhibitsED-SO values in the range' from 0.01 to 0.1 ppm. or lower, against bothA. oleracea and M. fructicola.

Part D To illustrate the effectiveness of the product of Part A as asoil fungicide via an expression of its ability to protect the seed andseedlings from seed decay and damping off fungicide (Pythium andFusarium species), infested soil, in 4" x 4" x 3" boxes, is treated bydrenching the soil with an aqueous formulation of the product of Part A.Treatment is accomplished by pouring a 32 lb./acre test formulation onthe surface of the soil. The thus-treated soil is allowed to stand forone day after which time it is removed from each box and thoroughlymixed before being replaced in the box.

Three days after this treatment, 25 pea seeds, variety Perfection, areplanted to a uniform depth in each box. As a control, seeds also areplanted in untreated soil and in sterilized soil. Percentage stand isrecorded 14 days after planting. Using this procedure at a concentrationof 32 lbs/acre, a percentage stand of 1% is obtained on the untreatedcontrol and a stand of on the sterilized control whereas a stand isobserved from using the test compound, thus indicating a singularly highsoil fungicidal activity.

Part E Beans, variety Tendergreen, and tomato, variety Bonny Best,plants growing in 4 pots are treated by pouring the formulation of theproduct of Part A at a concentration of 2000 ppm. into the pot at anequivalent rate of '128 lbs/acre (102 mg. per pot). Observation 9 and 14days after treatment shows both the tomato and bean plants,respectively, are killed. Further tests are conducted to demonstratephytotoxicity both by direct action, e.g., by spraying foliage, and bysystemic action, as indicated by soil watering tests. In the foliagespray test, tomato plants of thevariety Bonny Best, 5-7 tall, aresprayed with 100 m1. portions of a test formulation of the product ofPart A of this example at a concentration of 6400 ppm. After the sprayedplants are dried, they are removed to a greenhouse where they areobserved 14 days after treatment. Phytotoxicity is rated on a scale from0-11, 11 indicating complete kill. As a result of Part F Bactericidalactivity of the product of Part A is indicated using the test procedurereferred to in Part H of Example I with the exception that the bacteriaStaphylococcus aureus and Escherichia coli are used. Growth of the twoorganisms 48 hours after a 4-hour exposure to the test compound at aconcentration of 1000 ppm. is 25 and 40%, respectively, whereas .in acontrol, growths of 68% and 60%, respectively, are observed.

Part G Using the procedure referred to in Part D of Example I, ED-SOvalues of l-100 p.p.m. are obtained on the seeds of both the perennialrye grass and radish.

Part H Using the test procedure referred to in Part E of Example I, thefollowing data are obtained:

: Estimated Percentage Stand as Compared to Dosage, Lbs/Acre ControlBroadleat Grass 1 COO Part I Non-plant parasitic nematodes (Panagrellusredivivus) are exposed to the product of Part A in'small watch glasses(27 mm. diameter x 8 mm. deep) within a'9 cm. Petri dish and the resultsare recorded 24 hours after treatment. Using the above procedure, both a100% contact mortality and a 100% fumigant mortality at concentrationsof 1000 and 500 p.p.m. are observed.

Part I The procedure of Part K of the first example is repeated with theproduct of Part A of this example. The same high fumigant activity isobserved.

While compounds of the above invention may be employed in a variety ofapplications, biologically active or otherwise, when employed asbiologically active materials, it will be understood, of course, thatsuch compounds may be utilized in diverse formulations, both liquid andsolid, including finely-divided powders and granular materials as wellas liquids, e.g., solutions, concentrates, emulsifiable concentrates,slurries, and the like, depending upon the application intended and theformulation media desired.

Thus, it will be appreciated that compounds of this invention may beemployed to form biologically active substances containing suchcompounds as essential active ingredients thereof, which compositionsmay also include finely-divided dry or liquid diluents, extenders,fillers, conditioners, such as various clays, diatomaceous earth, talc,spent catalyst, alumina silica materials and such liquid solvents,diluents, etc. as water and various organic liquids such as kerosene,acetone, benzene, toluene, xylene, and other petroleum distillatefractions or mixtures thereof.

It is to be understood that although the invention has been describedwith specific reference to particular embodiments thereof, it is not tobe so limited, since changes and.alterations therein may be made whichare within 8-,- the full intended "scop'e'ot thisinvention as' definedby the appended claims.

What is claimed is:

l. The method of killing plant pests, microorganisms, insects and plantswhich-comprises contacting said posts with a pesticidal amount of acompound having the structure so} 4 px...

wherein X-is halogen, m is anumber from 2 to 6, inclusive, and n is anumber equal to (6-m). I

2. The method according to claim- 1 wherein said compound is3,3,4,5-tetrachloro 2,3 dihydrothiophene-l,ldioxide.

3. The method according to claim 1 wherein said compound is3,3,4-trichloro-2,3-dihydrothiophene-l,l-dioxide.

4. The method accordingto claim 1 wherein said compound is3,3,5-trichloro-2,3-dihydrothiophene-1,1-dioxide.

5. The method accordingto claim 1 wherein said compound is3,4-dichloro-2,3-dihydrothiophene-l,l-dioxide.

6. The method of regulating plant growth which comprises applying togrowing plants a herbicidal'amount of the composition of claim 1.

7. The method of regulating plantgrowth which comprises applyingtogrowing plants'a herbicidal amount of the composition of claim 2;

8. The method of regulating-plantgrowth which comprises applying togrowing plants a herbicidal amount of the composition'of claim 3.

9. The method of regulating plant growth which comprises applying togrowing plants a herbicidal-amount of the composition of claim 4.

10. The method of regulating plant growth which comprises applying togrowing plants a herbicidal amount of the composition of claim 5.

11. The method of killing microorganisms which comprises contacting saidmicroorganisms with a lethal amount of a compound of the formula:

m g if.

wherein X is halogen, m is a number from 3 to -6, inclusive, and n is anumber equal to (6-m).

12. The method according to claim 11 wherein the killing is effected viafurnigant action.

13. The method of killing nematodes which comprises contacting saidnematodes with a nematocidal amount of a compound having the structurethi ll-X,

wherein X is halogen, m is a number from 3 to 6, inclusive, and n is anumber equal to (6-m).

15. The method of killing fungi which comprises contacting said fungiwith a fungicidal amount of a compound having the structure:

t & m

wherein X is halogen, m is a number from 3 to 6, inclusive, and n is anumber equal to (6-m).

16. The method of killing insects which comprises contacting saidinsects with an insecticidal amount of a compound having the structure:

Hai-

wherein X is halogen, m is a number from 3 to 6, inclusive, and n is anumber equal to (6-m).

17. The method of killing plants which comprises con- 10 tacting saidplants with a herbicidal amount of a compound having the structure: 1

nn g g Xm whereinX is halogen, m is a number from 3 to 6, inclusive, andn is a number equal to (6-m).

' References Cited in the file of this patent UNITED STATES PATENTS2,504,099 Morris et al Apr. 18, 1950 2,928,766 Rosen Mar. 15, 19602,937,972 Bluestone et al. May 24, 1960 2,939,871 Pyne et a1 June 7,1960 2,957,887 Berkey et al Oct. 25, 1960 FOREIGN PATENTS 542,599Belgium Nov. 30, 1955 536,564 Canada Jan. 29, 1957 I

1. THE METHOD OF KILLING PLANT PESTS, MICROORGANISMS, INSECTS AND PLANT WHICH COMPRISES CONTACTING SAID PESTS WITH A PESTICIDAL AMOUNT OF A COMPOUND HAVING THE STRUCTURE 